Faculty Publications

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Highly fluorescent materials derived from ortho-vanillin: Structural, photophysical electrochemical and theoretical studies
(Elsevier B.V., 2019) Poojary, S.; Acharya, M.; Abdul Salam, A.A.; Kekuda, D.; Nayek, U.; Madan Kumar, S.; Vasudeva Adhikari, A.V.; Dhanya, D.
Small-molecule organic fluorophores are highly in demand attributed to their extensive prospective in material and biomedical applications. Particularly, luminescent ?-conjugated organic molecules that possess an efficient solid-state emission are excellent candidates for optoelectronic devices. Focusing on high demand of organic fluorophores, we herein report the synthesis of three organic fluorescent materials derived from o?vanillin, viz. an ester (F1), an azine (F2) and an azo dye (F3). Interestingly, F2 exhibited very intense luminescence in its aggregate phase due to the restriction in intra-molecular rotation (RIR), as demonstrated by solution thickening studies. Further, its Single Crystal X-ray Crystallography (SCXRD) study suggested the existence of various intra and inter molecular interactions and gave evidences for locked intra-molecular rotations of the benzene rings in the rigid conformation of the molecule. The bathochromic shift in fluorescence from solution to solid phase was confirmed by its thin-film emission spectrum, which evidences the formation of J-aggregates. The observed RIR, development of J-aggregates and high conjugation in F2 impart an excellent fluorescence in its aggregated state. Thin films of both F2 and F3 on ITO plates exhibited a bathochromic shift with a deep orange to red photoluminescence on UV excitation. Furthermore, the morphological characterization revealed the presence of clear dense grains in case of F2 and F3, while the DSC analysis indicated phase transitions of all the derivatives. As seen from dielectric measurement studies, the azo dye F3 exhibited the highest dielectric constant among the three derivatives. The electronic and photophysical data based on Density Functional Theory (DFT) and Time Dependent-DFT (TD-DFT) calculations are in agreement with the experimental results. All the above data clearly advocate that, the synthesized fluorophoric o?vanillin derivatives are excellent candidates for electro-optical devices. © 2018 Elsevier B.V.
Mechanism of Spiral Wave Unpinning in the Belousov-Zhabotinsky Reaction with a DC Electric Field
(American Chemical Society, 2022) Amrutha, S.V.; Sebastian, A.; Sibeesh, P.; Punacha, S.; Shajahan, T.K.
We study the mechanism of spiral wave unpinning in the Belousov-Zhabotinsky (BZ) reaction with a DC electric field. The unpinning is characterized by the phase of the spiral tip around the obstacle boundary at the time of unpinning. We systematically measure the unpinning phase as a function of the chirality of spiral rotation, the initial phase of the spiral, the size of the pinning obstacle, the direction, and the strength of the applied electric field. In both BZ experiments and simulations using the Oregonator model, we observe that the spiral wave always unpins at a fixed position with respect to the applied field. The wave unpins when the electric field component in the direction of the tip velocity of the spiral waves becomes equal to a threshold field strength. From these observations, we deduce a relation between the phase of unpinning, the size of the pinning obstacle, the strength, and the direction of the electric field, and it agrees with our observations. We conclude from our observations that a retarding 'electric force' on the chemical wave is responsible for the unpinning in the BZ medium. Our results indicate that the 'electric force' is more effective in unpinning when the wave moves away from the anode than when it is moving toward it. © 2022 American Chemical Society.
Effect of electric field chirality on the unpinning of chemical waves in the Belousov–Zhabotinsky reaction
(Elsevier Ltd, 2024) Sebastian, A.; Sibeesh, P.; Amrutha, S.V.; Punacha, S.; Shajahan, T.K.
We investigate the unpinning of chemical spiral waves attached to obstacles in the Belousov–Zhabotinsky (BZ) reaction using a Circularly Polarized Electric Field (CPEF). The unpinning is quantified by measuring the angle at which the spiral leaves the obstacle. Previously, we had found that the wave can unpin when the electric field along the direction of the spiral is above a threshold value. When we apply a DC field, this condition can be satisfied for a range of spiral phases, which we call the unpinning window (UW). With a CPEF, this UW moves either along the direction of the spiral (co-rotating) or against the spiral (counter-rotating). We find that when the field is co-rotating, it can take several rotations of the spiral to get unpinned. With a counter-rotating field, the spiral always unpins during the first rotation. We analyze how unpinning with CPEF depends on the electric field's relative speed, chirality, and strength using experiments and the Oregonator model. Our work helps to understand and control chemical waves. © 2024 Elsevier Ltd

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